Iminosulfur oxydifluorides and the process for their preparation



United States Patent 3,410,669 IMINOSULFUR OXYDIFLUORIDES AND THEPROCESS FOR THEIR PREPARATION Richard D. Cramer, Landenberg, Pa.,assignor to E. I. (in Pont de Nemours and Company, Wilmington, Del., acorporation of Delaware No Drawing. Continuation-impart of applicationSer. No. 820,115, June 15, 1959. This application May 8, 1963, Ser. No.278,998

Claims. (Cl. 23357) This application is a continuation-in-part of mycopending, coassigned application, Ser. No. 820,115, filed June 15,1959, now abandoned.

This invention relates to new compounds containing fluorine and to aprocess for preparing these compounds.

Compounds containing fluorine in chemical combination have achievedconsiderable technical importance in recent years because of unusualproperties. Thus, certain inorganic fluorides are highly reactivematerials and are used as fluorinating agents or as catalysts. Otherfluorinecontaining compounds, especially volatile fluorine compoundshaving fluorine bonded to oxygen-free carbon, are inert and are used asrefrigerants. Long chain compounds containing a plurality of fluorineatoms attached to carbon are generally characterized by a high degree ofchemical stability and are used as lubricants or lubricant additives.

The preparation and properties of compounds with fluorine-carbon bondshave been studied extensively but less attention has been given tocompounds containing a plurality of fluorine atoms attached to an atomother than carbon. Compounds containing carbon-nitrogen-sulfur bonds inwhich fluorine is bonded to a sulfur atom have been investigated to avery limited extent. Compounds are known which are referred to asiminosulfur difluorides (see US. 2,862,029) and which have the generalformula R-N SF These products are highly reactive compounds in which thesulfur is tetravalent and is free of oxygen, i.e., the sulfur is notbonded to oxygen. Compounds in which the sulfur is hexavalent and isbonded to an oxygen atom, a nitrogen atom and to two fluorine atoms areunknown.

The new class of compounds of the invention can be described genericallyas iminosulfur oxydifluorides. This class of compounds has acharacteristic feature a group which contains a hexavalent sulfur atomwhich is joined to an oxygen atom by a double bond, to a trivalentnitrogen atom by a double bond and to each of two fluorine atoms bysingle bonds. The characterizing group in these compounds is representedby the formula The new compounds of the invention are represented by thegeneral formula wherein X is hydrogen or an organic group. When X ishydrogen the compound has the formula 3,410,669 Patented Nov. 12, 1968i.e., it is iminosulfur oxydifluoride, the first and simplest compoundof the broad class of the compounds of the invention. When X is anorganic group (R), the compounds of the invention can be represented bythe formula The composition of the R group is not critical and it isdetermined primarily by the availability of the amines from which theiminosulfur oxydifluorides are obtained. Thus, R preferably is anorganic group of 1-18 carbons which is a hydrocarbon, a halohydrocarbonin which the halogens are of atomic number 9-35 (fluorine, chlorine andbromine), or a substituted hydrocarbon in which the only substituentsare at most two (i.e., 1-2) of the following groups: iminosulfuroxydifluoride [N=S(O)F carboxyl [--C(O)OH], nitro (-NO amino NHloweralkylamino [-NH(loweralkyl), -N(loweralky1) and hydroxyl (-O'H),each amino, loweralkylamino and hydroxyl group being bonded to a nuclearcarbon of an aromatic ring. The expression loweralkyl as used hereindenotes an alkyl group of less than eight carbons. It is also preferredthat the above hydrocarbon, halohydrocarbon or substituted hydrocarbongroups contain at most one olefinic or acetylenic bond, i.e., at mostone aliphatic C=C or CEC linkage. Compounds of the invention wherein Ris an aliphatically saturated hydrocarbon, halohydrocarbon orsubstituted hydrocarbon group as described above are particularlypreferred. By aliphatically saturated I means that the group is free of\oleflnic and acetylenic bonds and that it can contain aromaticunsatur'ation.

The preferred compositions of the R group, as described above, are basedsolely on cost and availability of the amine reactant. Thus, the totalnumber of carbons in R is not critical but a maximum of 18 carbons ispreferred because amines of this carbon content are generally available.The R group can be open chain, closed chain (i.e., cyclic) or acombination of open and closed chains. The open chain structure can be astraight or branched chain.

A class of especially preferred iminosulfur oxydifluorides are compoundsin which R contains at most 18 carbons and is an aliphatically saturatedhydrocarbon group (alkyl, cycloalkyl, aryl, alkaryl) or a substitutedaliphatically saturated hydrocarbon group in. which the alphacarbon,i.e., the carbon bonded to -N=S(O)F is unsubstituted [CH N=S(O)F thesubstituents on said R group being halogen of atomic number 9-35, or upto two groups which are iminosulfur oxydifluoride, carboxy, nitro, aminoor hydroxyl, each amino or hydroxyl group being bonded to a nuclearcarbon of an aromatic ring.

The following examples are illustrative of the broad range of thecompounds of the invention:

methyliminosulfur oxydifluoride, neopentyliminosulfur oxydifluoride,octyliminosulfur oxydifluoride, Z-ethylhexyliminosulfur oxydifluoride,cyclobutyliminosulfur oxydifluoride, cyclohexyliminosulfuroxydifluoride, 4-cyclohexylphenyliminosulfur oxydifluoride,4-cyclopentylphenyliminosulfur oxydifluoride,4-phenylcyclohexyliminosulfur oxydifluoride,2-decahydronaphthyliminosulfur oxydifluoride 2-anthryliminosulfuroxydifluoride, 4-biphenyliminosulfur oxydifluoride,S-acenaphtheniminosulfur oxydifluoride, Z-fluoreniminosulfuroxydifluoride, methallyliminosulfur oxydifluoride, crotyliminosulfuroxydifluoride,

octadecenyliminosulfur oxydifluoride, octynylirninosulfur oxydifluoride,

butynyliminosulfur oxydifluoride, 2-chloroethyliminosulfuroxydifluoride, 2,2,2-trifluoroethyliminosulfur oxydifluoride,1H,1H,5H-octafluoropentyliminosulfur oxydifluoride,3-bromopropyliminosulfur oxydifluoride, 8,8,8-trifluorooctyliminosulfuroxydifluoride, 4-carboxycyclohexyliminosulfur oxydifluoride,1H,lH-perfluorohexyliminosulfur oxydifluoride,4-nitrocyclohexyliminosulfur oxydifluoride, p-fluorophenyliminosulfuroxydifluoride, 2,4-dichlorophenyliminosulfur oxydifluoride,p-diethylarninophenyliminosulfur oxydifluoride,m-dihexylaminophenyliminosulfur oxydifluoride,p-methylaminophenyliminosulfur oxydifluoride,p-dimethylaminophenyliminosulfur oxydifluoride, p-nitrophenyliminosulfuroxydifluoride,

4-( 3'-nitrophenyl) -phenyliminosulfur oxydifluoride,4-(4'-nitrocyclohexyl)-phenyliminosulfur oxydifluoride,3,3-dichloro-4,4,4-trifluorobutyliminosulfur oxydifluoride,3-carboxy-2-hydroxyphenyliminosulfur oxydifluoride,5-nitro-3-hydroxyphenyliminosulfur oxydifluoride,4-carboxy-8-bromonaphthyliminosulfur oxydifluoride, and the like.

The compounds of the invention in which the nitrogen is bonded to anorganic group are colorless liquids or solids which have a generallypleasant odor. These compounds are free of the acrid odor normally foundin acid halides. However, the unsubstituted iminosulfur oxydifiuoride,i.e., HN S(O)F has a fairly sharp odor. The compounds are stablechemically and are not readily hydrolyzed by water. They are insolublein water but dissolve readily in the conventional organic solvents,e.g., acetone, benzene, ether, ethyl acetate, dimethylformamide,acetonitrile, and the like. The compounds hydrolyze only very slowly incontact with aqueous alkaline solution but will hydrolyze more rapidlyin a solvent for both the iminosulfur oxydifluon'de and the alkalinereagent. The excellent chemical stability of the iminosulfur oxydifluo-=rides of the invention is in marked contrast to the high chemicalreactivity disclosed in US. 2,862,029 for iminosulfur difluorides. Thecompounds of the invention can be stored in conventional containersunder ordinary conditions of temperature and humidity. It is notnecessary to take precautions to prevent access of moisture. Theiminosulfur oxydifluorides are relatively stable thermally.

The iminosulfur oxydifluorides are prepared by reacting thionyltetrafluoride (S01 with ammonia or a primary amine. It is not essential,however, that ammonia or the primary amines be used as the free bases.Thwe reactants can be used, if desired, in the form of their salts withorganic and inorganic acids. For simplicity of presentation, thenitrogen-bearing reactant will be :referred to as ammonia or an organicamine but it is intended to include within the scope of these terms thefree bases and their salts.

The process can also be described as the reaction of thionyltetrafluoride With a compound of the formula XNH (or itssalts) where Xis hydrogen or an organic radical, R, bonded to the nitrogen through acarbon atom. The mechanism of the reaction is not clearly understood butit can be represented by the following equation:

The reaction may, if desired, be conducted in the presence of a hydrogenfluoride acceptor, for example, an alkali metal fluoride such as sodiumfluoride, whereby the concentration of free hydrogen fluoride is kept ata mini- 'mum during the operation of the process.

Thionyl tetrafluoride, also called sulfur oxytetrafluoride, which isemployed as one reactant, is a gas boiling at -49 C. It can be preparedby fluorination of thionyl fluoride, as described by Dudley, Cady andEggers, J. Am.

.4 Chem. Soc, 78, 1553 (1956). Material which has been purified byconventional methods is satisfactory for use.

The nitrogen-bearing reactant, i.e., ammonia, organic amines or theirsalts, are commercially available materials which can be employed in theprocess without special purification. It is preferred that the reactantsbe substantially anhydrous but it is not essential that all traces ofwater be removed. The presence of minor amounts of water will not renderthe process inoperable.

The conditions which are used in the process are determined to someextent by the nature of the iminosulfur oxydifluoride which is beingprepared. Preparation of the simplest iminosulfur oxydifluoride, i.e.,HN=S(O)F requires more careful control of conditions, particularly withrespect to temperature, than the preparation of nitrogen-substitutediminosulfur oxydifluorides, i.e., compounds of the structure RN=S(O)FThe conditions for preparing both types of compounds are discussed morefully in the following paragraphs.

The simplest compound of the invention, i.e., iminosulfur oxydifluoride,is prepared by reacting ammonia (or an ammonium salt of an organic orinorganic acid) and thionyl tetrafluoride at a low temperature,preferably at about the melting point of carbon dioxide in the presenceof a neutral (i.e., neither acidic nor basic) oxygenated liquid reactionmedium in which the oxygen is present as an oxy linkage. A reactiontemperature of less than 50 C. is especially preferred to obtain maximumyield of the desired product. When the reaction is conducted attemperatures higher than about -30 C., Whether in the presence orabsence of an oxygenated liquid reaction medium, the principal productis a polymer and no measureable quantity of iminosulfur oxydifluoride,i.e., HN S(O)F is obtained. The reaction can be represented by thefollowing equation:

The preferred reaction medium for the reaction of ammonia (or its salts)and thionyl tetrafluoride is an organic ether in which the ether oxygenis bonded to hydrocarbon groups of at least two carbons each. Especiallypreferred are hydrocarbon ethers in which the hydrocarbon groups aresaturated and have from 26 carbons. Cyclic ethers can be employedalthough open chain ethers are preferred. Examples of operable ethersare diethyl ether, diisopropyl ether, ethyl butyl ether, dicyclopropylether, dicyclohexyl ether, tetrahydrofuran and dioxane.

The order in which the reactants are added in the process is notcritical. The ammonia and thionyl tetrafluoride may be added separatelyin any order to the reaction medium or the reactants can be addedsimultaneously. In one mode of operation of the process, the desiredquantity of liquid ammonia is dissolved in the ether solvent at a lowtemperature, e.g., 50 to C., and thionyl tetrafluoride is addedgradually to the stirred ammonia-ether solution. Reaction is rapid andreaches completion in a relatively short time. The reaction mixture isworked up by conventional methods, e.g., filtration and distillation,and iminosulfur oxydifluoride is obtained rnost conveniently as anazeotrope with ether which boils at 5758 C. Th molar ratio of ethylether to iminosulfur oxydifiuoride in the azeotrope is about 0.85:1.Iminosulfur oxydifluoride can be obtained in pure form from theazeotrope by a number of methods, e.g., by vapor phase chromatography orby forming a complex of the ether with boron trifluoride and separatingthe iminosulfur oxydifluoride by distillation. Pure iminosulfuroxydifiuoride is a colorless liquid boiling at 4344 C.

The nitrogen-substituted compounds of the invention, i.e., compounds ofthe formula RNfl(O)F where R has the meaning described previously, areobtained by the reaction of primary amines (or their salts with organicand inorganic acids) with thionyl tetrafluoride. The discussion whichfollows applies to the process employing a primary amine (in contrast toammonia, discussed earlier) and thionyl tetrafluoride.

The primary amines suitable for reaction with thionyl tetrafluorideaccording to the process of this invention are of the formula R'NH whereR is a 'rnonovalent organic group. It is preferred, of course, that theorganic group be free of substituents, other than -NH which may reactwith thionyl tetrafluoride or the iminosulfur oxydifluoride group underthe conditions of the process and thus lead to a substantial reductionin the yield of desired iminosulfur oxydifluoride. To illustrate, Rshould be free of aliphatically bonded hydroxyl and loweralkylaminogroups. By the term aliphatically-bonded I means the substituents arebonded to carbons which are members of aliphatic and cycloaliphaticgroups. Compounds which are free of the aliphatically-bondedsubstituents named above are readily prepared and easily purified.Compounds having hydroxyl and loweralkylamino groups bonded to nuclearcarbons of aromatic groups are operable and are included in theinvention.

In the preferred primary amines, represented by the formula RNH R is anorganic group of 118 carbons which is a hydrocarbon, a halohydrocarbonin which the halogens are of atomic number 9-35 (fluorine, chlorine andbromine), or a substituted hydrocarbon in which the only substituents,in addition to the -NH group already present, are at most two (i.e.,1-2), of the following groups: carboxyl, nitro, amino, mono anddi(loweralkyl)amino and hydroxyl, each monoand di(loweralkyl)amino andhydroxyl group being bonded to nuclear carbon of an aromatic ring. WhenR is thus defined, the reaction can be represented by the followingequation:

where R is as previously defined. As is by now apparent, R and R will beidentical unless R contains primary amine groups which react withthionyl tetrafiuoride.

As in the case of R, it is preferred that R contain at most one olefinicor acetylenic bond, with aliphatically saturated R groups beingparticularly preferred.

An especially preferred class of primary amine reactants are those inwhich R contains at most 18 carbons and is an aliphatically saturatedhydrocarbon group or substituted aliphatically saturated hydrocarbongroup in which alphacarbon, i.e., the carbon bonded to -NH isunsubstituted [-CH NH the substituents on said R group being halogen ofatomic number 9-35 or 1 to 2 members of the group consisting of amino,carboxy, nitro and hydroxy, each hydroxy group being bonded to a nuclearcarbon of an aromatic ring.

The primary amine reactant can, of course, have more than one primaryamine group, e.g., two, three or even a greater number of NHsubstituents can be present. In the case of aliphatic compounnds whichhave a plurality of NH substituents, all of the primary aminesubstituents generally react with thionyl tetrafluoride to ob tain acompound which has a plurality of iminosulfur oxydifluoride groups. Inthe case of aromatic amines having two or more primary aminesubstituents, products are obtained in which one or more than one of theprimary amine substituents have reacted with thionyl tetrafiuoride.

It is possible, therefore, to prepare aromatic iminosulfuroxydifluorides having a primary amine substituent bonded to a nuclearcarbon. In general, substituents (other than primary amine) bonded tocarbons of an aromatic ring do not enter into the reaction with thionyltetrafluoride. Secondary and tertiary amine groups, e.g., C H NH- and (CH N-, bonded to nuclear aromatic carbon do not enter into the reaction,and these groups appear in the final product.

It is not essential that a solvent be employed in the reactionof aprimary amine with thionyl tetrafiuoride. Solvents can, of course, beemployed as a matter of convenience to facilitate handling of thereactants and to control the temperature or the rate of the reaction.Solvents, if used, should be inert or non-reactive with any of thecomponents present in the process. Examples of suitable solvents areether, benzene, acetonitrile and acetone.

The temperature at which the primary amine (R'NH and thionyltetrafiuoride are reacted is not critical. In general, the temperatureis kept as low as possible and it should not exceed thedisproportionation temperature of thionyl tetrafluoride which is about450 C. The temperature may lie between about C. and about 250 C.Satisfactory yields of iminosulfur oxydifluorides are usually obtainedat a temperature lying between about 20 and C.

The molar ratio in which the reactants (either ammonia or amine and SOFare employed is not critical and operable molar ratios may cover a widerange, for example, the ratio, expressed as moles of NH groups/moles ofSOF may lie between about 0.05 and about 20. For maximum yields ofiminosulfur oxydifluorides, the preferred molar ratios will be dependentto some extent on the nature and reactivity of the amine reactant. Thus,when an aliphatic amine is employed as a reactant, it is preferred thatthe molar ratio, NH groups/S01 should be no greater than about 4. When ahigher molar ratio of aliphatic amine to SOF is employed, iminosulfuroxyditluorides are obtained but in reduced yield and the reactionrequires more careful control than when a lower molar ratio of reactantsis employed. When an aromatic amine is used as a reactant the maximummolar ratio, NH groups/S01 can be high Without adverse effect on theyield of iminosulfur oxydifluoride. In general, satisfactory yields ofthe desired product are obtained by employing a molar ratio which liesbetween about 0.5 and 4.0.

The process is generally conducted in reaction vessels from which moistair is preferably excluded by conven' tional means. The inner surface ofthe reaction chamber is preferably made of corrosion-resistant material,e.g., glass or a nickel-iron-molybdenum alloy known commercially asHastelloy C. Rigorous exclusion of moisture is not essential, and, infact, the process will operate in the presence of moist air although theyield of desired product may be reduced.

The pressure under which the reaction is conducted is not critical. Whenthe process is conducted under pressure, the reaction vessel isgenerally chilled to a low temperature, e.g., in a solid carbondioxide/acetone bath, and is then flushed with nitrogen. The reactionvessel is charged with the nitrogen-containing reactant and with thionyltetraflouride. The reaction vessel is closed and heated under autogenouspressure with suitable mechanical agitation at a temperature and for aperiod of time necessary to effect reaction. The reaction generallyproceeds rapidly and is completed in a relatively short time.

When the process is conducted at atmospheric presure, the reactionvessel is equipped with tubes containing drying agents to excludeexcessively moist air and with one or more condensers to prevent escapeof low boiling materials, e.g., thionyl tetrafiuoride. The reactor isgenerally cooled to a low temperature and is charged with a solvent andthen nitrogen-bearing reactant. Thionyl tetrafluoride is then led intothe reaction chamber through an inlet tube which terminates above thesurface of the reaction mixture. The reaction mixture is preferablystirred vigorously during the process.

In either mode of operation the reaction mixture is generally filteredat the end of the operation, and the filtrate is washed with water andalkaline solution to remove acidic by-products. The solvent, if present,is removed by distillation, and the residue is fractionally distilledunder reduced pressure to obtain the pure product. Other conventionaland well known methods of purification can be employed, e.g.,distillation in a molecular still, vapor phase and liquid phasechromatography and fractional crystallization at low temperatures.

The invention is illustrated in greater detail in the followingexamples, in which parts are by weight unless otherwise indicated.

EXAMPLE I A glass reaction vessel (capacity, 1000 parts of water),fitted with a mechanical stirrer, thermometer and gas inlet tube, iscooled to about 80" C. and is charged with about 175 parts of ether and1.7 parts of liquid ammonia. The solution is stirred and maintained at-55 C. and 12.4 parts of thionyl tetrafluoride is passed into the vesselover a period of 15 minutes. A thick white solid forms which partiallyredissolves as the reaction proceeds. The mixture is allowed to warm toabout 25 C. in a 3-hour period, and the supernatant liquid is decanted.This liquid is distilled through an efiicient fractionating column, andthere is obtained about 4.7 parts of a liquid boiling at 55-58 C.Redistillation of the liquid product yields 3.7 parts of a clear liquid,boiling at 575 C. The nuclear magnetic resonance spectra for proton andfor fluorine and elementary analyses show that the product is a constantboiling azeotrope of iminosulfur oxydifluoride, (HN S(O)F and ether. Theelemental analysis of this product is as follows: C, 25.56; H, 6.00; N,8.82; S, 19.43; F, 22.17.

Ammonia and thionyl tetrafluoride are passed separately into about 210parts of ether at 30 to 40 C. for 25 minutes. The ammonia is passed inat a rate of 0.2 part by volume/minute and thionyl tetrafluoride at arate of about 0.09 part by volume/minute. The mixture is allowed to warmto about 25 C. and is then filtered. The filtrate is fractionallydistilled to yield 4.7 parts of the azeotrope of iminosulfuroxydifluoride and ether, boiling at 575 C.; n 1.3395. The elementalanalysis on this product is as folows: C, 25.28; H, 6.25; F, 24.30; N,9.40; S, 19.66.

The analyses of the products obtained in Part A and Part B show that theratio of ether to iminosulfur oxydifluoride in the liquid product isapproximately 0.84: 0.03, i.e., approximately 0.85 mole of ether ispresent for each mole of iminosulfur oxydifluoride and the approximateformula of the liquid product is HN"-S(O) F -O.85C H OC H A glasspolymer tube (capacity, 25 parts of water) is charged with 5.5 parts ofthe azeotrope obtained as described in Part A, and an equimolar quantityof boron trifluoride is condensed in the tube. The tube is sealed andstored for 16 hours at 78 C. It is then opened, and the contents,chilled to 78 C., are fractionally distilled at 0.04 mm. pressure. Nodistillate is obtained at 78 C. but on gradual warming about 0.3 part ofcolorless liquid is obtained at 33" C. and, at 0 C., 3-4 parts ofcolorless liquid are collected in the receiver. Redistillation of thisfraction at atmospheric pressure yields 1.7 parts of iminosulfuroxydifluoride, a stable colorless liquid of sharp odor, boiling at 44C., 11 1.3223; d =l.5246. The identity of the compound is confirmed bynuclear magnetic resonance and infrared absorption spectra and byelemental analysis.

Analysis.Calcd for HNS(O)F N, 13.86; S, 31.72; F, 37.59. Found: N,14.46; S, 32.45; F, 37.96.

EXAMPLE II A glass reactor of the type described in Example I is chargedwith 3.7 parts of ammonium fluoride, 12 parts of sodium fluoride andabout 110 parts of diethyl ether. The mixture is chilled to 78 C. andapproximately 12.5 parts of thionyl tetrafluoride is passed into thereactor with vigorous stirring of the reaction mixture over a period of20 minutes. The reaction mixture is allowed to warm to about 25 C. overa period of 15-18 hours and it is then filtered. The filtrate isdistilled through an efficient fractionating column to obtain 3.1 partsof the iminosulfur oxydifluoride-ether azeotrope boiling at 5757.5 C.The iminosulfur oxydifluoride is separated from the azeotrope by theprocess described in Example I, Part C. The pure compound is alsoseparated by vapor phase chromatography employing a heat stable silicone(B.P. 185 C.) on firebrick.

By employing the process described in Example II, thionyl tetrafluoridecan be reacted with ammonium salts of organic and inorganic acids toobtain iminosulfur oxydifluoride. Examples of salts which can beemployed are ammonium chloride, ammonium nitrate, ammonium sulfate,ammonium phosphate, ammonium acetate, ammonium butyrate, ammonuimbenzoate, and the like. The preferred salts are the readily availablecommercial products such as ammonuim chloride.

EXAMPLE III A pressure reaction vessel (capacity, 400 parts of water)lined with Hastelloy C is flushed with nitrogen gas and cooled in asolid carbon dioxide/acetone solution. The vessel is then charged with 8parts of methylamine and 31 parts of thionyl tetrafluoride. The chargedvessel is sealed, and it is then heated to -104 C. for 16 hours. Thereaction vessel, cooled to about 25 C., is connected to an evacuatedstainless steel cylinder which is chilled in a solid carbon dioxide/acetone bath, and the low boiling reaction products are distilled intothe stainless steel cylinder. There is obtained 27.5 parts of reactionproducts.

The above reaction is repeated employing 16 parts of methylamine and 31parts of thionyl tetrafluoride, and there is obtained 13.2 parts ofreaction products.

The reaction products of the two runs are combined, and they aredistilled in a fractional distillation apparatus over sodium fluoride. Avolatile material, boiling at -39 C. is removed initially after whichthere is obtained 14 parts of methyliminosulfur oxydifluoride boiling at39 C. The structure of the compound, which is CH N=S(O)F is confirmed bythe infrared and nuclear magnetic resonance spectra, by the massspectrum and by elemental analysis.

Analysis.-Calcd for CH NSOF C, 10.8; H, 2.61; N, 12.2; S, 27.9; F, 33.0.Found: C, 10.22; H, 2.53; N, 11.18; S, 27.55; F, 32.61.

EXAMPLE IV In this procedure there is employed a glass reaction vessel(capacity, 1000 parts of Water) which is equipped with a condensercooled with a solid carbon dioxide/ acetone solution, a dropping funneland a mechanically driven stirrer. The reaction vessel is chilled in asolid carbon dioxide/acetone bath, and the vessel is charged withapproximately 36 parts of ether and 31 parts of thionyl tetrafluoride.To this chilled solution there is added over a period of 1 hour withvigorous stirring a solution of 7.5 parts of ethylenediamine in about 40parts of ethyl ether. A white solid separates from the mixture duringthe reaction. After addition of the diamine solution is completed, thereaction vessel is warmed to 10 C. for 4 hours and then allowed to standfor 15 hours at 25 C. The reaction mixture is poured onto chopped ice,and the etheral solution is separated. This solution is washedsuccessively with aqueous dilute alkali solution, dilute hydrochlorideacid solution and water. The etheral solution is dried over anhydrousmagnesium sulfate, filtered and the ether is removed by evaporation. Theliquid residue is distilled in an eflicient fractionating unit to obtain6 parts of ethylenebis(iminosulfur oxydi- 9 fluoride), boiling at 52C./1l mm, The identity of the compound, which has the formula isconfirmed by the infrared spectrum and by elemental analysis.

Analysis.-Calcd for C H N O S F C, 12.3; H, 1.75; N, 12.4. Found: C,11.47; H, 1.96; N, 11.37.

Examples III and IV illustrate the compounds of the invention in whichthe R group is aliphatic hydrocarbon, and their preparation The processis generic for the preparation of this class of compounds and can beemployed with aliphatic open and closed chain primary amines bearing atleast one -NH group. The R group can be alkyl, alkenyl, alkynyl,cycloalkyl, cycloalkenyl or a combination of these structures. Toillustrate, by employing the process of Examples III and IV, thionyltetrafluoride can be reacted with ethylamine to obtain ethyliminosulfuroxydifluoride, with 2-ethylhexylamine to obtain 2-ethylhexyliminosulfuroxydifluoride, with dodecylamine to obtain dodecylimino-sulfuroxydifluoride, with octadecylamine to obtain octadecyliminosulfuroxydifluoride, with allylamine to obtain allyliminosulfur oxydifluoride,with methallylamine to obtain methallyliminosulfur oxydifluoride, withoctenylamine to obtain octenyliminosulfur oxydifluoride, with2-propynylamine to obtain propynyliminosulfur oxydifluoride, withbutynylamine to obtain butynyliminosulfur oxydifluoride, withcyclohexylamine to obtain cyclohexyliminosulfur oxydifluoride, with4-allylcyclohexylamine to obtain 4- allylcyclohexyliminosulfuroxydifluoride, with 1,3-diaminopropane to obtain 1,3propylenebisfiminosulfur oxydifluoride), with 1,6 diaminohexane toobtain 1,6- hexamethylenebis(iminosulfur oxydifiuoride), with 1,4-diaminocyclohexane to obtain 1,4-cyclohexylbis(iminosulfuroxydifiuoride), with 1,3,5-triaminocyclohexane to obtain1,3,5-cyclohexyltris(irninosulfur oxydifluoride) and withcyclohexenylamine to obtain cyclohexenyliminosulfur oxydifiuoride.

EXAMPLE V A reaction vessel, similar to the reactor described in ExampleIV, is charged with 33 parts of E-aminocaproic acid and about 78 partsof acetonitrile. The suspension of the acid in acetonitrile is stirredvigorously at about 25 C., and there is added 31 parts of thionyltetrafluoride over a period of about 0.75 hour. The reaction mixturebecomes warm initially, but it later becomes cool. The aminocaproic aciddissolves as the reaction proceeds. The reaction mixture is poured intoice water, ether is added, and the ether-acetonitrile solution isseparated. This solution is washed with water, 100 parts of water isadded, and 20 M sodium hydroxide solution is carefully added withstirring until the solution becomes alkaline. The aqueous solution isseparated, filtered and concentrated to a small volume under reducedpressure. The concentrated solution is acidified carefully with dilutehydrochloric acid, and there is obtained 6.5 parts of5-carboXy-n-pentyl-iminosulfur oxydifluoride, an oil which solidifieswhen chilled and melts at about 0 C. The compound is purified by vacuumsublimation (bath temperature, 50 0.; pressure, 2 mm.) into a condenserchilled with a solid carbon dioxide/acetone solution. The purifiedproduct is a colorless oil at room temperature; neutral equivalent:calculated, 215; found, 215. The identity of the compound which has thestructure is confirmed by the infrared absorption spectrum.

Example V illustrates the compounds of the invention, and theirpreparation, in which the R group is a substituted aliphatic hydrocarbonbearing subsfiituents which are inert to or unreactive with theiminosulfur oxidifiuoride group. Such substituents are, of course,unreactive with thionyl tetrafluoride. The process is generic for thepreparation of this class of compounds and can be employed withaliphatic open and closed chain primary amines bearing inertsubstituents. The R groups can be substituted alkyl, alkenyl, alkynyl,cycloalkyl, cycloalkenyl or a combination of these structures in whichthe substituents are halogens of atomic number 9-35, carboxyl and nitrogroups as well as iminosulfur oxydifluoride groups. The primaryaliphatic amines employed in the process can have as substitutents, inaddition to primary amine groups, halogens of atomic number 9 35,carboxyl and nitro groups. To illustrate, thionyl tetrafluoride can bereacted with fluoropropylamine to obtain fluoropro pyliminosulfuroxydifluoride, with trifiuoromethylcyclohexylamine to obtaintrifluoromethylcyclohexyliminosulfur oxydifluoride, withbromocyclohexylamine to obtain bromocyclohexyliminosulfur oxydifluoride,with bromocyclohexylmethylamine to obtain bromocyclohexylmethyhiminosulfur oxydifluoride, with nitrohexylamine to ob tainnitrohexyliminosulfur oxydifluoride, with d initrocyclohexylamine toobtain dinitrocyclohexyliminosulfur oxydifluoride, witha1lylchlorocyclohexylamine to obtain allylchlorocyclohexyl iminosulfuroxydifluoride, with 3- carboxypropylarnine to obtain3-carboxypropylimino-sulfur oxydifluoride, with glycine to obtaincarboxymethyliminosulfur oxydifluoride, withcarboxydecahydronaphthylamine to obtaincarboxydecahydronaphthyliminosulfur oxydifiuoride and withfl-(di-carboxy)ethylamine to obtain [5-(di-carboxy)ethyliminosulfuroxydifluoride.

EXAMPLE VI A pressure reaction vessel, similar to the reactor employedin Example III, is charged with 46.5 parts of aniline. The vessel isclosed, chilled in a solid carbon d ioxide/acetone solution andevacuated to a low pressure. The vessel is then charged with 31 parts ofthionyl tetrafiuoride, and the reaction mixture is heated at 100 C. for16 hours. After cooling to about 25 C. the vessel is opened, and theliquid reaction product is transferred to an efficient fractionaldistillation unit. The product is distilled under reduced pressure andyields 16 parts of phenyliminosulfur oxydifluoride, a colorless liquidwhich boils at 62 C./ 26 1mm.; n 1.4751. The identity of the compound,which has the structure C H N=S(O)F is confirmed by the infraredabsorption spectrum.

A glass reaction vessel (capacity, 500 parts of water) equipped asdescribed in Example II, is chilled in a solid carbon dioxide/ acetonebath and charged with 31 parts of thionyl tetrafiuoride and about 71parts of ethyl ether. Aniline (46 parts) is added through the droppingfunnel at a controlled rate. The reaction is vigorous initially andrefluxing occurs. About one-half the aniline is added over a 30-minuteperiod, and the remainder is added over a Ill-minute period when thevigor of the reaction is subsiding. The reaction mixture is poured ontochopped ice, and the ethereal solution is separated. The solution iswashed successively with cold aqueous hydrochloric acid and water, andit is then dried over anhydrous magnesium sulfate. The ether solution isfiltered, the ether removed by evaporation, and the liquid residue isdistilled to obtain 35 parts of phenyliminosulfur oxydifluoride.

Phenyliminosulfur oxydifluoride is a chemically stable compound whichcan be chlorinated by conventional procedures to yieldp-chlorophenyliminosulfur oxydifluoride, a colorless liquid, boiling at98 C./35 mm.; n

' 1,0532. The identity of the chlorophenyl compound is confirmed by itsinfrared absorption spectrum.

EXAMPLE VII Using a pressure vessel and procedure as described inExample III, a mixture of 13.5 parts of p-phenylenediamine and 31 partsof thionyl tetrafiuoride is heated at 75 C. for 15.5 hours. There isobtained a fuming reaction product which is a heavy black tar with someblack mobile liquid. The mixture is poured onto chopped ice using etheras a washing solvent to transfer the product from the reaction vessel.The resulting tarry mixture is made alkaline with aqueous sodiumhydroxide, and the original tar becomes quite fluid. The etherealsolution is separated, washed with water and dried over anhydrousmagnesium sulfate. The solution is filtered and warmed to remove theether. The liquid residue is distilled to yield parts ofp-phenylenebis-(iminosulfur oxydifluoride), a colorless liquid boilingat 54 C./1 mm. The identity of the compound, which has the formula isconfirmed by the infrared absorption spectrum and by elemental analysis.

Anaylsis.-C'alcd. f0rC H N S O F C, 26.1; H, 1.45; N, 10.2; S, 23.2; F,27.5. Found: C, 26.49; H, 1.47; N, 10.45; S, 23.44; F, 27.87.

A glass reaction vessel (capacity, 1000 parts of Water), fitted asdescribed in Example IV, except that the dropping funnel is replaced bya gas inlet tube, is charged with 54 parts of p-phenylenediamine andabout 310 parts of acetonitrile. Thionyl tetrafluoride (124 parts) ispassed into the reaction vessel, with vigorous stirring, over a periodof 1 hour. The reaction mixture becomes warm, and a solid productseparates which dissolves almost completely as the reaction proceeds.The reaction mixture is poured onto ice, and about 140 parts of ether isadded with stirring. Solid sodium sulfate is added to assist inseparating the reaction product. The ether layer is separated and washedtwice with aqueous hydrochloric acid solution containing sodium sulfateand twice with aqueous sodium sulfate solution. The ether solution isfiltered and dried over anhydrous sodium sulfate. Distillation of theethereal solution yields 92 parts of p-phenylenebis(iminosulfuroxydifluoride), boiling at 5254 C./ 1 mm.

EXAMPLE VIII A glass reaction vessel of the type described in ExampleVII, Part B, is charged with 13.5 parts of o-phenylenediamine and about105 parts of ethyl ether. The reaction vessel and contents are cooled inan ice bath, and 31 parts of thionyl tetrafluoride is added over aperiod of 1 hour. The reaction mixture is poured into ice Water, and theethereal layer is separated. It is washed successively with aqueoushydrochloric acid and Water. The ethereal layer is dried over anhydrousmagnesium sulfate and filtered. The filtrate is distilled through aneflicient fractionating column to yield 21 parts ofo-phenylenebis-(iminosulfur oxydifluoride), B.P. 55 C./8 mm. Theidentity of the product is confirmed by the infrared absorptionspectrum.

EXAMPLE IX A glass reactor of the type described in Example VII, Part B,is charged With 54 parts of m-phenylenediamine and 75-80 parts ofacetonitrile, and 31 parts of thionyl tetrafluoride is added to thesolution over a period of 0.5 hour. The reaction mixture is poured ontoice; about 150 parts of ether are added together with sodium sulfate toexpedite separation of the mixture into two layers. The ethereal layeris separated, and the remaining aqueous layer is extracted with ether.The ethereal solutions are combined and washed successively with aqueoushydrochloric acid and water. The ethereal layer is dried over magnesiumsulfate, filtered and then distilled through an efficient fractionatingcolumn to yield 13 parts of mphenylenebis-(iminosulfur oxydifiuoride),Bil, 53 C./

2 mm. The identity of the compound is confirmed by the infraredabsorption spectrum and by elemental analysis.

Analysis.Calcd for C6H4F4N2O2S2: c, 26.1; H, 1.45; N, 10.1. Found: c,26.73; H, 1.62; N, 10.55.

A glass reaction vessel, as described in Example VII, Part B, is chargedwith 54 parts of m-phenylenediamine and l55160 parts of acetonitrile.The reaction vessel and solution is chilled in ice Water, and 31 partsof thionyl tetrafiuoride is added to the solution over a period of 1hour. The reaction mixture is poured into ice water, and concentratedaqueous sodium sulfate solution is added to the mixture to effect aseparation of the acetonitrile and aqueous phases. The aqueous phase isremoved, washed with ether and chilled in an ice bath. About parts ofether is added to the aqueous solution, and the solution is then madealkaline by adding a 10% solution of sodium hydroxide at such a ratethat the temperature does not rise above 25 C. The ethereal layer isseparated and dried over anhydrous magnesium sulfate. One-fourth of thedried ethereal solution is saturated with hydrogen chloride gas, and thehydrochloride of m-aminophenyliminosulfur oxydifluoride precipitates asan orange-colored solid The solid product is separated by filtration anddried in air. It is soluble in water and absolute ethanol and sparinglysoluble in ethyl acetate. The compound is insoluble in ether. Theidentity of the product is confirmed by its infrared absorption spectrumand by analysis.

Analysits.Calcd for c,H,F N os-Hc1= c, 31.5; H, 3.06; N, 12.3. Found: C,33.60; H, 3.74; N, 13.24.

The remaining portion of the ethereal solution is warmed under reducedpressure, and the residue (8 parts) is distilled in a molecular still ata pressure of approximately 0.01 mm. and at a temperature of 40 C. Apale yellow liquid is obtained which is m-aminophenyliminosulfuroxydifiuoride The identity of the compound is confirmed by the nuclearmagnetic resonance and infrared absorption spectra.

Examples VI-IX illustrate the compounds of the invention, and theirpreparation, in which R is an aryl hydrocarbon group. The process isgeneric for the preparation of this type of compound and can be employedwith single ring primary amines or with primary amines containing aplurality of aryl rings which can be separate or fused. The R groups canbear hydrocarbon group's bonded to nuclear aryl carbons. To illustrate,thionyl tetrafluoride can be reacted with 2,5-xylidene to obtain2,5-xylyliminosulfur oxydifluoride, with naphthylamine to obtainnaphthyliminosulfur oxydifluoride, with 4-arninobiphenyl to obtainbiphenylyliminosulfur oxydifluoride, with 4-aminodiphenylmethane toobtain 4-benzy1phenyliminosulfur oxydifluoride, withcyclohexylphenylamine to obtain cyclohexylphenyliminosulfuroxydifluoride and with allylphenylamine to obtain allylphenyliminosulfuroxydifluoride.

EXAMPLE X A reaction vessel similar to the reactor employed in ExampleVII, Part B, is charged with 25.5 parts of p-aminophenol and about 78parts of acetonitrile. The reactor and contents are cooled in an icebath, and 29 parts of thionyl tetrafluoride is added over a period of 1hour. The reaction mixture is stirred for 4 hours and is then pouredonto a mixture of ethyl ether and ice water with vigorous stirring. Themixture is rendered neutral by addition of aqueous sodium bicarbonatesolution, and the ethereal layer is separated. The ethereal layer isdried over magnesium sulfate and filtered. The ether is removed underreduced pressure, care being taken to keep the temperature of theresidue in the still pot below 25 C. There is obtained a dark oilyresidue which is soluble in aqueous sodium hydroxide but insoluble inWater. The oily product forms a purple color when added to ferricchloride solution there- 13 by showing its phenolic character. The crudeoil is distilled at a pressure of about 0.01 mm. of mercury and at atemperature of 45 C. to yield 15 parts of p-hydroxyphenyliminosulfuroxydifluoride. The identity of the product is confirmed by the infraredabsorption spectrum and by elemental analysis.

Analysis.Calcd for C H F O NS: C, 37.3; H, 2.58; H, 19.2. Found: C,36.30; H, 2.82; F, 18.32.

EXAMPLE XI A reaction vessel of the type described in Example VII, PartB, is charged with 69 parts of m-nitroaniline and about 140 parts ofethyl ether. The reactor and contents are cooled in ice water, and 62parts of thionyl tetrafluoride is added over a period of about 1 hour.The reaction mixture is stirred for 5 hours as the temperature isallowed to rise to about 25 C. and it is then poured onto ice water. Theheterogeneous mixture is filtered to remove a small amount ofprecipitated material, and the ethereal layer is separated. This layeris washed with aqueous dilute hydrochloric acid and then with Water. Theethereal layer is dried over anhydrous magnesium sulfate, filtered andit is then distilled through an efficient fractionating column. There isobtained 7 parts of mnitrophenyliminosulfur oxydifiuoride, a liquidwhich boils at 71 C./ 1.5 mm. pressure. The identity of the product isconfirmed by the infrared absorption spectrum and by elemental analysis.

Analysis.-Calcd C H F N O S: C, 32.4; H, 1.8; F, 17.1. Found: C, 33.12;H, 2.01; F, 16.54.

Examples X and XI illustrate the compounds of the invention in which Ris an aryl group bearing substituents, other than hydrocarbon, which areunreactive or inert to thionyl tetrafluoride. The process is generic forthe preparation of this class of compounds and can be employed withmonocyclic or polycyclic aryl compounds bearing substituents which arehalogen, amino, loweralkylamino, carboxy, hydroxy or nitro. Toillustrate, thionyl tetrafluoride can be reacted with2,4-dichloroaniline to obtain 2,4-dichlorophenyliminosulfuroxydifluoride, with trifluoroaniline to obtaintrifluorophenyliminosulfur oxydifiuoride, with p-(p'-bromobenzyl)anilineto obtain p- (p'-bromobenzyl) phenyliminosulfur oxydifluoride, withpethylaminoaniline to obtain p-ethylaminophenyliminosulfuroxydifluoride, with p-(p'-dimethylaminophenyl) aniline to obtainp-(p-dimethylaminophenyl)phenyliminosulfur oxydifluoride, withm-aminobenzoic acid to obtain mcarboxyphenyliminosulfur oxydifluoride,with 2,4-dinitroaniline to obtain 2,4-dinitrophenyliminosulfuroxydifiuoride, and with triaminobenzene to obtain aminophenylbis-(iminosulfur oxydifiuoride) The example which follows illustrates theprocess of the invention employing a salt of a primary amine as thereactant.

EXAMPLE XII A glass reaction vessel of the type described in ExampleVII, Part B, is charged with 23 parts of aniline and about 145 parts ofdiethyl ether. Hydrogen chloride gas is then passed into the solutionuntil all of the aniline is converted to insoluble anilinehydrochloride. The suspension of aniline hydrochloride in ether isstirred vigorously and 31 parts of thionyl tetrafluoride is passed intothe reaction mixture. The temperature of the mixture is maintained at lto 0 C. by the refluxing of the thionyl tetrafluoride for a period of 24hours. The reaction mixture is poured onto ice and the ethereal solutionis separated. It is Washed with cold 10% hydrochloric acid and with icewater. The ethereal solution is dried, filtered and then distilledthrough an efficient fractionating column. There is obtained 8 parts ofphenyliminosulfur oxydifluoride, B.P. 68 C./3 mm.; 11 1.4750.

Aniline hydrofluoride (C H NH -HF) reacts with thionyl tetrafluorideunder the conditions described in Example XII to yield phenyliminosulfuroxydifiuoride. In like manner, thionyl tetrafluoride reacts withethylamine hydrochloride to yield ethyliminosulfur oxydifluoride, withbutylammonium acetate to yield butyliminosulfur oxydifluoride and withcyclohexylammonium propionate to yield cyclohexyliminosulfuroxydifiuoride.

Example XII illustrates the process of the invention employing a salt ofthe primary amine as the reactant. The process is generic for thepreparation of iminosulfur oxydifluorides. The salt is an acid additioncompound between the primary amine and the acid. The salt serves solelyas a carrier of the amine and is a convenient means of introducing theamine into the reaction zone. The acid portion of the salt does notenter into or interfere with the reaction. For practical and economicalreasons the simplest acid addition salts are employed, e.g., salts ofinorganic halogen acids such as hydrochloric acid, hydrobromic acid,salts of phosphoric and sulfuric acids, salts of readily availableorganic acids, such as acetic, benzoic, trichloroacetic and the like.

The compounds of the invention are useful as solvents for highlyfiuorinated polymers, e.g., the fiuorinated olefin polymers. Solutionsof such polymers, e.g., poly- (tetrafluoroethylene polychlorotrifiuoroethylene) and the like in iminosulfur oxydifluorides areuseful in making cellulosic compositions water-repellant. To illustrate,an approximately 10% by weight solution of a low molecular weight, lowmelting tetratluoroethylene polymer (melting range 83150 C.) is preparedby warming the polymer in methyliminosulfur oxydifiuoride until thepolymer dissolves. Strips of filter paper are treated with thissolution, either by immersion in the liquid or by pouring the liquid onthe paper. The treated paper, optionally washed with acetone, is driedin air. The treated paper is not wet by drops of water whereas untreatedpaper is immediately and completely wetted by water. The treated paperdoes not support combustion whereas the untreated paper burns readily.Equally good results are obtained by employing approximately 10%solutions of low-melting tetrafiuoroethylene polymer in iminosulfuroxydifiuoride, S-carboxy-n-pentyliminosulfur oxydifluoride andphenyliminosulfur oxydifiuoride.

High boiling iminosulfur oxydifluorides are generically useful asmodifiers for polymeric products to improve the flexibility of filmsobtained from the polymers. To illustrate, films of polystyrenecontaining about 10% of m-nitrophenyliminosulfur oxydifluoride showsubstantially better resistance to cracking on flexing than films fromunmodified polystyrene.

Since obvious modifications and equivalents in the invention will beevident to those skilled in the chemical arts, I propose to be boundsolely by the appended claims.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A compound of the formula X-N=S(O)F wherein X contains up to 18carbons and is a member of the group consisting of hydrogen,hydrocarbon, halohydrocarbon in which all halogens are of atomic number9-35, and substituted hydrocarbon having as its sole substituents 1-2members of the class consisting of -N=S(O)F carboxyl, nitro, amino,NH(loweralkyl), -N(loweralkyl) and hydroxyl, each amino,-NH(loweralkyl), -N(loweralkyl) and hydroxyl group being bonded to anuclear carbon of an aromatic ring.

2. A compound of claim 1 wherein X is hydrocarbon.

3. A compound of claim 1 wherein X is aliphatically saturatedhydrocarbon.

. Methyliminosulfur oxydifiuoride.

. Ethylenebis (iminosulfur oxydifiuoride) Phenyliminosulfuroxydifluoride.

. m-Aminophenyliminosulfur oxydifluoride. m-Nitrophenylirninosulfuroxydifiuoride.

. Iminosulfur oxydifiuoride.

10. A process of preparing a compound of the formula RN:S(O)F wherein Rcontains 1-18 carbons and is a member of the group consisting ofhydrocarbon, halohydrocarbon in which all halogens are of atomic number935, and substituted hydrocarbon having as its sole substitutents 1-2members of the class consisting N:S(O)F carboxyl, nitro, amino,NH(loweralky1), -N(loweralkyl) and hydroxyl, each amino,-NH(loweralkyl), N(loweralkyl) and hydroxyl group being bonded to anuclear carbon of an aromatic ring,

which comprises contacting thionyl tetrafiuoride with an amine of theformula RNH at a temperature between about -80 C. and about 250 C. undersubstantially anhydrous conditions,

R being an organic group of 1-18 carbons selected from the groupconsisting of hydrocarbon, halohydrocarbon in which all halogens are ofatomic number 93 5, and substituted hydrocarbon having as its solesubstituents 1-2 members of the class consisting of carboxyl, nitro,amino, -NH(loweralkyl), -N(loweralkyl) and hydroxyl, eachNH(loweralkyl), -N(loweralkyl) and hydroxyl group being bonded to anuclear carbon of an aromatic ring.

11. The process of claim 10 wherein the temperature is between about-2() C. and 150 C.

12. The process of claim 10 wherein said amine is used in the form ofone of its acid addition salts.

13. A process of preparing iminosulfur oxydifiuoride comprising reactingthionyl tetrafiuoride with ammonia at a temperature below about -30 C.in the presence of a neutral oxygenated liquid reaction medium in whichthe oxygen is present as an oxy linkage.

14. The process of claim 13 wherein the temperature is below 50 C.

15. The process of claim 13 wherein the ammonia is used in the form ofone of its acid addition salts.

References Cited UNITED STATES PATENTS Glemser et al.: Zeitschrift fur,Anorganische and Allgemeine Chemie, vol. 284, pp. 97100, 1956.

EDWARD J. MEROS, Primary Examiner.

1. A COMPOUND OF THE FORMULA X-N=S(O)F2, WHEREIN X CONTAINS UP TO 18CARBONS AND IS A MEMBER OF THE GROUP CONSISTING OF HYDROGEN,HYDROCARBON, HALOHYDROCARBON IN WHICH ALL HALOGENS ARE OF ATOMIC NUMBER9-35, AND SUBSTITUTED HYDROCARBON HAVING AS ITS SOLE SUBSTITUENTS 1-2MEMBERS OF THE CLASS CONSISTING OF -N=S(O)F2, CARBOXYL, NITRO, AMINO,-NH(LOWERALKYL), -N(LOWERALKYL)2, AND HYDROXYL, EACH AMINO,-NH(LOWERALKYL), -N(LOWERALKYL)2 AND HYDROXYL GROUP BEING BONDED TO ANUCLEAR CARBON OF AN AROMATIC RING.